KR101405871B1 - Method for preparing polyester blends with high molecular weight and polyester blends produced with the same - Google Patents
Method for preparing polyester blends with high molecular weight and polyester blends produced with the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2467/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
Abstract
컴파운딩과 고상중합(solid state polymerization)을 통하여 고분자량을 가지는 폴리에스테르 블렌드의 제조방법이 개시된다. 상기 폴리에스테르 블렌드의 제조방법은 (a) 폴리에틸렌테레프탈레이트(PET)에 글리콜 변성 폴리(1,4-싸이클로헥산디메탄올 테레프탈레이트) 코폴리에스테르(PCTG)를 컴파운딩하여 PET/PCTG 블렌드 칩을 얻는 단계, 및 (b) 얻어진 PET/PCTG 블렌드 칩을 결정화시킨 후, 고상중합하여 분자량을 상승시키는 단계를 포함하며, 상기 PET는 테레프탈릭 애시드, 에틸렌글리콜 및/또는 탄소수 3 내지 6의 알킬렌글리콜로 이루어진 PET, 또는 상기 PET 성분에 이소프탈릭 애시드, 싸이클로헥산디메탄올(CHDM) 또는 디에틸렌글리콜이, 애시드(acid) 또는 디올(diol) 성분에 대하여 1 내지 10mol% 공중합된 PET이고, 상기 PCTG에서 CHDM 함량은 디올 성분에 대하여 40 내지 100mol%이고, 에틸렌글리콜 함량은 디올 성분에 대하여 0 내지 60mol%이다.A process for producing a polyester blend having a high molecular weight through compounding and solid state polymerization is disclosed. The method for producing the polyester blend includes (a) obtaining a PET / PCTG blend chip by compounding glycol-modified poly (1,4-cyclohexanedimethanol terephthalate) copolyester (PCTG) with polyethylene terephthalate And (b) crystallizing the obtained PET / PCTG blend chip and then increasing the molecular weight by solid-phase addition, wherein the PET is selected from the group consisting of terephthalic acid, ethylene glycol, and / or alkylene glycol having 3 to 6 carbon atoms Or PET in which 1 to 10 mol% of isophthalic acid, cyclohexane dimethanol (CHDM) or diethylene glycol is copolymerized with an acid or diol component in the PET component, and CHDM The content is 40 to 100 mol% with respect to the diol component, and the ethylene glycol content is 0 to 60 mol% with respect to the diol component.
PET, PETG, PCTG, 고상중합, 고유점도 PET, PETG, PCTG, solid phase polymerization, intrinsic viscosity
Description
본 발명은 고분자량을 가지는 폴리에스테르 블렌드의 제조방법에 관한 것으로서, 더욱 상세하게는 컴파운딩과 고상중합을 통하여 고분자량을 가지는 폴리에스테르 블렌드의 제조방법 및 이를 이용하여 제조된 폴리에스테르 블렌드에 관한 것이다.The present invention relates to a process for producing a polyester blend having a high molecular weight and more particularly to a process for producing a polyester blend having a high molecular weight through compounding and solid phase polymerization and a polyester blend prepared using the same .
폴리에스테르는 기계적 강도, 내열성, 투명성 및 가스 배리어성(gas barrier property)이 우수하기 때문에, 특히 주스, 청량 음료, 탄산 음료 등의 음료 충전용 용기나, 포장용 필름, 오디오, 비디오용 필름 등의 소재로서 가장 적합하여 대량으로 사용되고 있다. 또한, 의료용 섬유나 타이어코드 등의 산업자재로서도 세계적인 규모로 사용되고 있다.Polyesters are excellent in mechanical strength, heat resistance, transparency and gas barrier properties, and are therefore particularly suitable for containers for beverage filling such as juice, soft drinks and carbonated drinks, packaging films, audio and video films And is used in large quantities. It is also used as industrial materials such as medical fibers and tire cords on a global scale.
이러한 폴리에스테르의 종류에는 여러 가지가 있으나, 상업적으로 가장 많이 사용되고 있는 것은 PET이다. PET는 기체 차단성이 우수하고 상업생산이 활발하게 이루어지고 있어 다양한 종류의 음식료 포장재의 재료로 폭넓게 사용되고 있으나, 유리전이온도와 용융점 사이의 온도 환경에서 열 이력을 받게 되면 결정이 생기고 이로 인해 투명성이 훼손되는 단점이 있다. 이러한 PET의 단점 때문에 PET가 적용될 수 있는 투명한 제품의 두께에 제한을 받게 되며, 통상적으로 압출공정에 의해 시트(sheet)를 생산할 경우에는 2 내지 3mm가 생산 가능한 시트 두께로 알려져 있다. 이러한 한계를 극복하기 위하여, PET 공중합을 통하여 PET의 결정화 속도를 느리게 하는데, 이소프탈릭 애시드(isophthalic acid, IPA) 공중합 PET, 싸이클로헥산디메탄올(CHDM) 공중합 PET 등이 이에 해당된다. 또한, 일정 비율 이상으로 공중합하여 PET의 결정화 성질을 본질적으로 제거함으로써, 무정형(amorphous) 폴리에스테르를 만들기도 하는데, 사용된 전체 디올에 대하여 20 내지 60 mol%의 CHDM으로 공중합한 PETG(glycol modified PET copolyester)의 경우가 이에 해당된다.There are many kinds of such polyesters, but PET is the most widely used commercially. PET is widely used as a material for various food and beverage packaging materials because it has excellent gas barrier properties and commercial production is active. However, when a thermal history is obtained in a temperature environment between a glass transition temperature and a melting point, crystals are formed, There is a disadvantage that it is damaged. Due to the disadvantage of such PET, the thickness of the transparent product to which PET can be applied is limited, and when a sheet is produced by an extrusion process, it is known that the sheet thickness is 2 to 3 mm. In order to overcome these limitations, the crystallization rate of PET is slowed down through PET copolymerization, such as isophthalic acid (IPA) copolymerized PET, and cyclohexanedimethanol (CHDM) copolymerized PET. In addition, amorphous polyester may be produced by copolymerizing at a predetermined ratio or more to essentially eliminate the crystallization property of PET. In the case of using glycol modified PET (PETG) copolymerized with 20 to 60 mol% copolyester).
그러나, PETG는 무정형이므로 결정이 생기지 않기 때문에, 유리전이온도 이상이 되면 유리(glass) 상태에서 고무(rubbery) 상태를 거쳐 열적 내구성이 떨어진다. 따라서, PETG는 PET의 경우와 달리, 200℃ 내외의 온도에서 중합도를 더 상승시키는 고상중합(solid state polymerization)이 불가능하므로, 목표로 하는 분자량이나 고유점도를 용융상태에서 얻어야 하는 제약이 있다. 반면에, PET의 경우, 고유점도 0.5 내지 0.7 dl/g을 얻기 위해서는 용융상태로 중합하고, 고유점도 0.8 내지 1.0 dl/g을 얻기 위해서는, 용융중합으로 얻은 고분자 PET를 결정화시킨 다음, 고체 부분결정 상태에서 200 내지 220℃의 온도에서 추가로 중합(고상중합)시키어, 요구되는 중합도를 얻는다. 이러한 이유로 고분자량, 즉 고유점도 0.80 dl/g 이상의 PETG를 얻기는 쉽지 않으며, 이를 위하여는 적합한 반응기 구조, 촉매 및 안정제의 사용이 요구된다.However, since PETG is amorphous, no crystals are formed. When the glass transition temperature is higher than the glass transition temperature, the glassy state undergoes a rubbery state and the thermal durability is degraded. Therefore, unlike the case of PET, PETG has a limitation in obtaining a desired molecular weight or intrinsic viscosity in a molten state since it is impossible to perform solid state polymerization in which the polymerization degree is further raised at a temperature of about 200 ° C or so. On the other hand, in the case of PET, in order to obtain an intrinsic viscosity of 0.5 to 0.7 dl / g, the polymer is polymerized in a molten state to obtain an intrinsic viscosity of 0.8 to 1.0 dl / g. After crystallizing the polymer PET obtained by melt polymerization, (Solid-state polymerization) at a temperature of 200 to 220 캜 in the state of a polymerization initiator to obtain a desired degree of polymerization. For this reason, it is not easy to obtain PETG having a high molecular weight, that is, an intrinsic viscosity of 0.80 dl / g or more. To this end, it is required to use a suitable reactor structure, catalyst and stabilizer.
PET는 압출, 사출 가능한 폴리에스테르 수지로서, 가정용품, 음식료 용기, 가전제품 부품, 자동차 부품 등 다양한 용도의 재료로 사용되고 있다. 이중 빛에 대한 투과성이 요구되는, 즉 투명도가 요구되는 제품을 얻기 위한 방법으로는, PET의 조성 중 디애시드(diacid) 성분 또는 디올(diol) 성분을 이소프탈릭 애시드, CHDM 등의 제3의 물질로 치환하여 중합한 코폴리에스테르(공중합 폴리에스테르)를 사용하는 기술이 공지되어 있으며, 이러한 기술을 이용한 다양한 PET 및 PETG 제품이 사용되고 있다. 상기 코폴리에스테르는 PET 자체의 결정화 속도를 낮추거나, 결정화되지 않도록 폴리머 물성을 변화시키어, 투명 제품의 생산을 유리하게 한다.PET is an extrudable and extrudable polyester resin that is used as a material for various applications such as housewares, food containers, home appliance parts, and automobile parts. As a method for obtaining a product requiring transparency to double light, that is, a product requiring transparency, it is possible to use a diacid component or a diol component in the composition of PET as a third material such as isophthalic acid, CHDM (Copolyester) polymerized by substitution with a substituent is known, and various PET and PETG products using such a technique are used. The copolyester lowers the crystallization rate of the PET itself or changes the physical properties of the polymer so as not to be crystallized, thereby favoring the production of a transparent product.
상기 방법 이외에도, 제품의 투명도를 향상시키는 방법으로서, PET/PETG 블렌드 및 PET/PCTG 블렌드 기술, 즉 PET와, 공중합 정도가 높은 공중합물인 PETG 또는 PCTG(glycol modified poly(1,4-cyclohexylenedimethylene terephthalate) copolyester)를 블렌딩하는 방법이 개시되어 있다(미국특허 제5,382,628호, 미국특허 제4,263,364호, 미국특허 제4,897,448호 등). 그러나, 이러한 통상적인 블렌드 기술은 두 가지 이상의 폴리머를 용융(melt) 상태에서 물리적 혼합 및 일부 화학적 반응에 의하여 블렌딩하는 기술을 개시할 뿐, 블렌드의 중합도 및 분자량이 각 재료의 본래 분자량으로 제한되는 문제를 극복하는 기술에 대해서는 아직까지 공지된 바가 없다.In addition to the above methods, PET / PETG blend and PET / PCTG blend technique, that is PET and copolymers with high degree of copolymerization, such as PETG or PCTG (glycol modified poly (1,4-cyclohexylenedimethylene terephthalate) (U.S. Patent No. 5,382,628, U.S. Patent No. 4,263,364, U.S. Patent No. 4,897,448, etc.). However, this conventional blend technique only discloses a technique of blending two or more polymers by physical mixing and some chemical reaction in a melt state, and the problem that the polymerization degree and molecular weight of the blend are limited to the original molecular weight of each material Has not yet been known.
한편, 아세트알데히드(acetaldehyde)는 폴리에스테르의 열분해 반응의 결과 생성되는 휘발성 물질로서, 폴리머 재료가 식품 및 음료 용기의 재료로 사용될 경우, 내용물의 맛에 영향을 주게 되므로, 그 함량을 일정한 수준 이하로 관리할 필요가 있다.On the other hand, acetaldehyde is a volatile substance produced as a result of the pyrolysis reaction of polyester. When the polymer material is used as a material for food and beverage containers, it affects the taste of the contents, Need to manage.
따라서 본 발명의 목적은 PETG와 유사한 조성을 가지면서도, 고유점도 0.8 dl/g 이상의 고중합도를 가지며, 폴리머 내의 아세트알데히드 함량이 낮은 폴리에스테르 블렌드를 제조하는 방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for producing a polyester blend having a composition similar to that of PETG, but having a high polymerization degree of an intrinsic viscosity of 0.8 dl / g or more and a low acetaldehyde content in the polymer.
상기 목적을 달성하기 위하여, 본 발명은 (a) PET에 PCTG를 컴파운딩하여 PET/PCTG 블렌드 칩을 얻는 단계, 및 (b) 얻어진 PET/PCTG 블렌드 칩을 결정화시킨 후, 고상중합하여 분자량을 상승시키는 단계를 포함하며, 상기 PET는 테레프탈릭 애시드, 에틸렌글리콜 및/또는 탄소수 3 내지 6의 알킬렌글리콜로 이루어진 PET, 또는 상기 PET 성분에 이소프탈릭 애시드, CHDM 또는 디에틸렌글리콜이, 애시드 또는 디올 성분에 대하여 1 내지 10mol% 공중합된 PET이고, 상기 PCTG에서 CHDM 함량은 디올 성분에 대하여 40 내지 100mol%이고, 에틸렌글리콜 함량은 디올 성분에 대하여 0 내지 60mol%인 것인 폴리에스테르 블렌드의 제조방법을 제공한다. 여기서, 상기 PET의 함량은 전체 블렌드에 대하여 50 내지 95중량%이고, 상기 PCTG의 함량은 전체 블렌드에 대하여 5 내지 50중량%인 것이 바람직하다. 본 발명은 또한 상기 방법에 따라 제조된 폴리에스테르 블렌드를 제공한다.In order to achieve the above object, the present invention provides a process for producing a PET / PCTG blend chip, comprising: (a) obtaining a PET / PCTG blend chip by compounding PCTG on PET; and (b) crystallizing the PET / PCTG blend chip obtained, Wherein the PET is PET comprising terephthalic acid, ethylene glycol and / or an alkylene glycol having 3 to 6 carbon atoms, or an isophthalic acid, CHDM or diethylene glycol to the PET component, an acid or diol component Wherein the CHDM content in the PCTG is from 40 to 100 mol% based on the diol component and the ethylene glycol content is from 0 to 60 mol% based on the diol component. do. Here, the content of the PET is 50 to 95% by weight with respect to the total blend, and the content of the PCTG is preferably 5 to 50% by weight with respect to the total blend. The present invention also provides a polyester blend prepared according to the process.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명자는 PETG 조성을 가지면서 고유점도가 0.8 dl/g 이상인 폴리에스테르를 얻는 방법에 대하여 연구한 결과, 결정성 수지인 PET와 비결정성 수지인 PCTG를 일정비율로 용융상태로 컴파운딩하여 블렌드 칩을 얻은 후, 블렌드 칩을 다시 고상중합하면, 폴리에스테르 중 CHDM 함량이 PETG의 경우와 유사하면서도, 고유점도가 0.80 dl/g 이상인 폴리에스테르를 얻을 수 있음을 발견하였다. 뿐만 아니라, 상기 방법에 따르면, 기존의 단순한 컴파운딩 방법으로 생산된 블렌드보다 폴리머 내부에 존재하는 아세트알데히드 성분의 함량을 획기적으로 줄일 수 있다는 점을 발견하였다.The inventors of the present invention have studied a method of obtaining a polyester having an intrinsic viscosity of 0.8 dl / g or more while having a PETG composition. As a result, it has been found that blending a blend of PET, which is a crystalline resin, and PCTG, , And then blending the blend chips again in the solid phase, it was found that a polyester having an intrinsic viscosity of 0.80 dl / g or more can be obtained, while the CHDM content in the polyester is similar to that of PETG. In addition, according to the above method, it was found that the content of the acetaldehyde component present in the polymer can be drastically reduced as compared with the blend produced by the conventional simple compounding method.
구체적으로, 본 발명에 따른 폴리에스테르 블렌드의 제조방법은 (a) PET에 PCTG를 컴파운딩하여 PET/PCTG 블렌드 칩을 얻는 단계, 및 (b) 얻어진 PET/PCTG 블렌드 칩을 결정화시킨 후, 고상중합하여 분자량을 상승시키는 단계를 포함한다. 상기 (b)단계에서 결정화는 140 내지 180 ℃에서 블렌드 칩을 2 내지 6 시간 동안 방치 또는 유지시켜 수행하는 것이 바람직하다. 만일 블렌드 칩의 결정화가 충분하지 않으면, 향후 고상중합 과정에서 블렌드 칩이 융착될 우려가 있고, 블렌드 칩의 결정화가 과도하게 수행되면 경제적으로 불리할 뿐 특별한 이익이 없다. 또한, 결정화된 블렌드 칩의 고상중합은 180 내지 230℃에서 5 내지 15 시간 동안 수행하는 것이 바람직하다. 만일, 상기 고상중합이 충분하지 않으면, 블렌드 칩의 고유점도가 충분히 증가하지 않는 문제가 있고, 상기 고상중합이 과도하게 수행되면 성형공정의 온도를 과도하게 올려야 하는 문제가 있다. Specifically, the process for producing a polyester blend according to the present invention comprises the steps of (a) compounding PCTG with PET to obtain a PET / PCTG blend chip, and (b) crystallizing the PET / PCTG blend chip obtained, Thereby increasing the molecular weight. In the step (b), it is preferable that the crystallization is performed by allowing or maintaining the blend chip at 140 to 180 ° C for 2 to 6 hours. If the crystallization of the blend chip is not sufficient, there is a possibility that the blend chip is fused in the solid phase polymerization process in the future, and if the crystallization of the blend chip is excessively performed, there is no particular advantage that it is disadvantageous economically. In addition, the solid state polymerization of the crystallized blend chip is preferably performed at 180 to 230 캜 for 5 to 15 hours. If the solid state polymerization is insufficient, there is a problem that the intrinsic viscosity of the blend chip is not sufficiently increased. If the solid state polymerization is carried out excessively, there is a problem that the temperature of the molding process must be increased excessively.
상기 사용되는 PET는 테레프탈릭 애시드, 에틸렌글리콜 및/또는 탄소수 3 내지 6의 알킬렌글리콜로 이루어진 PET이거나, 또는 상기 PET 성분에 이소프탈릭 애시드, CHDM 또는 디에틸렌글리콜이, 애시드 또는 디올 성분에 대하여 1 내지 10mol% 공중합된 PET일 수 있다. 여기서, 이소프탈릭 애시드가 공중합되는 경우, 그 함량은 상기 공중합된 PET의 전체 애시드 성분에 대하여 1 내지 10mol%이며, CHDM 또는 디에틸렌글리콜이 공중합되는 경우, 그 함량은 상기 공중합된 PET의 전체 디올 성분에 대하여 1 내지 10mol%이다. 상기 PET의 함량은 전체 블렌드에 대하여 50 내지 95중량%인 것이 바람직하다. 상기 PET의 함량이 50중량% 미만이면 고상중합시 융착 현상이 발생하기 쉽고, 95중량%를 초과하면 높은 결정화 속도로 인해 가공후 제품 단계에서의 투명도를 떨어뜨리기 때문에 바람직하지 못하다.Wherein the PET used is PET consisting of terephthalic acid, ethylene glycol and / or alkylene glycols having 3 to 6 carbon atoms, or isotactic acid, CHDM or diethylene glycol is added to the PET component, 1 is added to the acid or diol component To 10 mol% copolymerized PET. When the isophthalic acid is copolymerized, the content thereof is 1 to 10 mol% based on the total amount of the acid component of the copolymerized PET, and when CHDM or diethylene glycol is copolymerized, the content thereof is the total diol component Based on the total weight of the composition. The content of the PET is preferably 50 to 95% by weight based on the total blend. When the content of PET is less than 50% by weight, fusion-bond phenomenon tends to occur during solid-state polymerization, and when it exceeds 95% by weight, transparency in a product stage after processing is lowered due to a high crystallization rate.
본 발명에서 사용되는 PCTG에서 CHDM 함량은, PCTG의 전체 디올 성분에 대하여 40 내지 100mol%이고, 에틸렌글리콜 함량은 0 내지 60mol%이다. 상기 PCTG의 함량은 전체 블렌드에 대하여 5 내지 50중량%인 것이 바람직하다. 상기 PCTG의 함량이 전체 블렌드에 대하여 5중량% 미만이면 가공후 제품의 투명도를 떨어뜨릴 우려가 있고, 50중량%를 초과하면 경제적 측면에서 재료비가 상승하고 제품의 색상이 황변되기 쉬우므로 바람직하지 못하다.The CHDM content in the PCTG used in the present invention is 40 to 100 mol% based on the total diol component of PCTG and the ethylene glycol content is 0 to 60 mol%. The content of the PCTG is preferably 5 to 50% by weight based on the total blend. If the content of PCTG is less than 5% by weight based on the total blend, there is a fear that the transparency of the product after processing is lowered. If the content is more than 50% by weight, the cost of the product is increased economically and the color of the product tends to be yellowed. .
상술한 바와 같은 본 발명의 방법에 따라 제조된 폴리에스테르 블렌드는, 고유점도가 0.60 dl/g 이상, 바람직하게는 0.80 dl/g 이상이며, CHDM 함량이 전체 블렌드의 디올 성분에 대하여 10 내지 40mol%, 바람직하게는 10 내지 30mol%이고, 아세트알데히드 함량이 3ppm 이하, 바람직하게는 1ppm 이하이다.The polyester blend prepared according to the method of the present invention as described above has an intrinsic viscosity of 0.60 dl / g or more, preferably 0.80 dl / g or more, and a CHDM content of 10 to 40 mol% based on the diol component of the entire blend. , Preferably 10 to 30 mol%, and the acetaldehyde content is 3 ppm or less, preferably 1 ppm or less.
본 발명에 따른 폴리에스테르 블렌드의 제조방법에 따르면, PETG와 유사한 공중합물 조성을 가지면서도, 고유점도 0.85 dl/g 이상의 고분자량을 갖는 폴리에스테르를 얻을 수 있으므로, 다양한 용도에 부합되는 폴리에스테르 제품을 효과적으로 제조할 수 있는 장점이 있다.According to the process for producing a polyester blend according to the present invention, a polyester having a copolymer composition similar to that of PETG and having a high molecular weight of an intrinsic viscosity of 0.85 dl / g or more can be obtained. Thus, There is an advantage that it can be manufactured.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail by way of examples. The following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by these examples.
하기 실시예에서 사용된 PET는 에스케이케미칼에서 생산하는 SKYPET BR grade(이하 성분 A, CHDM이 전체 디올에 대하여 3 내지 10 mol% 공중합된 PET)이었고, PCTG로는 에스케이케미칼에서 생산하는 J2003 grade(CHDM 함량: 디올 성분에 대하여 50 내지 80 mol%, 이하 성분 B)을 사용하였다. 하기 비교예에서 사용된 PETG로는 에스케이케미칼에서 생산하는 SKYGREEN PETG(CHDM 함량: 디올 성분에 대하여 약 20 내지 40 mol%)을 사용하였다.The PET used in the following examples was SKYPET BR grade (component A, CHDM copolymerized with 3 to 10 mol% of total diol copolymerized with PET) produced by SK Chemicals, and PCTG was J2003 grade (CHDM content : 50 to 80 mol%, relative to the diol component, component B) was used. As the PETG used in the following Comparative Examples, SKYGREEN PETG (CHDM content: about 20 to 40 mol% based on the diol component) produced by SK Chemicals was used.
[실시예 1] [Example 1]
제습 건조기를 사용하여 160℃에서 5시간 동안 건조한 성분 A 1.5kg, 및 동일한 제습 건조기에서 80℃로 5시간 동안 건조한 성분 B 1.5kg을 펠렛 상태에서 충분히 혼합하였다. 혼합된 원료를 하케사에서 제작한 압출기(Haake Extruder)를 통하여, 270℃, 50rpm의 조건에서 컴파운딩하고, 블렌드 칩을 제조하였다. 제조된 블렌드 칩을 120℃에서 결정화시키고, 결정화된 블렌드 칩 3kg을 200℃ 질소 대류형 고상중합 반응기를 사용하여 7시간 동안 고상중합하였다. 고상중합 전후의 블렌드 칩의 고유점도는 각각 0.73 dl/g, 0.90 dl/g으로, 0.17 dl/g의 고유점도가 상승함 을 확인하였다. 고상중합된 블렌드 칩에 대하여 NMR 분석을 실시한 결과, 블렌드의 전체 디올 몰수에 대하여, CHDM이 30mol%, 디에틸렌글리콜(diethylene glycol, DEG)이 약 5mol% 함유되어 있음을 확인하였다. 또한, 고상중합된 블렌드 칩을 동결분쇄한 후 칩내 함유된 아세트알데히드 함량을 측정한 결과, 0.7 ppm이었다.Using a dehumidifying dryer, 1.5 kg of Component A dried at 160 ° C for 5 hours and 1.5 kg of Component B dried at 80 ° C for 5 hours in the same dehumidifying dryer were thoroughly mixed in the pellet state. The mixed raw materials were compounded through an extruder (Haake Extruder) manufactured by Hasegawa at 270 DEG C and 50 rpm to prepare blend chips. The prepared blend chip was crystallized at 120 캜, and 3 kg of the crystallized blend chip was solid-phase polymerized at 200 캜 using a nitrogen-convection type solid-state polymerization reactor for 7 hours. The intrinsic viscosities of the blend chips before and after the solid phase polymerization were 0.73 dl / g and 0.90 dl / g, respectively, and the intrinsic viscosity of 0.17 dl / g was increased. NMR analysis was performed on the solid polymerized blend chip. As a result, it was confirmed that CHDM was contained in an amount of 30 mol% and diethylene glycol (DEG) was contained in an amount of about 5 mol% based on the total number of moles of the blend. Further, the content of acetaldehyde contained in the chip after freeze-pulverization of the solid-polymerized blend chip was found to be 0.7 ppm.
[실시예 2] [Example 2]
성분 A 및 성분 B의 사용량을 각각 2kg 및 1kg으로 달리한 것을 제외하고는, 실시예 1과 동일한 방법으로 컴파운딩하여 블렌드 칩을 얻고, 결정화 및 고상중합을 수행하였다. 고상중합 전후의 블렌드 칩의 고유점도는 각각 0.72 dl/g, 0.87 dl/g으로, 0.15 dl/g의 고유점도가 상승함을 확인하였다. 고상중합된 블렌드 칩에 대하여 NMR 분석을 실시한 결과, 블렌드의 전체 디올 몰수에 대하여, CHDM이 20mol%, 디에틸렌글리콜(diethylene glycol, DEG)이 약 5mol% 함유되어 있음을 확인하였다. 또한, 블렌드 칩을 동결분쇄한 후 칩내 함유된 아세트알데히드 함량을 측정한 결과, 0.8 ppm이었다.A blend chip was obtained by compounding in the same manner as in Example 1 except that the amounts of the components A and B were changed to 2 kg and 1 kg, respectively, and crystallization and solid phase polymerization were carried out. The intrinsic viscosities of the blend chips before and after the solid phase polymerization were 0.72 dl / g and 0.87 dl / g, respectively, and the intrinsic viscosity of 0.15 dl / g was increased. NMR analysis was conducted on the solid polymerized blend chip. As a result, 20 mol% of CHDM and about 5 mol% of diethylene glycol (DEG) were contained relative to the total number of moles of the blend. The content of acetaldehyde contained in the chip after freeze-disintegration of the blend chip was 0.8 ppm.
[비교예] [Comparative Example]
PETG 3kg에 대하여 고상중합을 진행하기 위하여, 온도를 120℃까지 올렸으나, 결정화가 일어나지 않았고, 펠렛 간에 서로 융착되는 현상으로 인해, 고상중합을 진행할 수 없었다. 고상중합 전 고유점도는 0.76 dl/g이었고, 블렌드 칩을 동결분쇄한 후 칩내 함유된 아세트알데히드 함량을 측정한 결과, 35.0 ppm이었다.In order to proceed the solid phase polymerization to 3 kg of PETG, the temperature was raised to 120 캜, but the crystallization did not occur, and the solid phase polymerization could not proceed due to fusion between the pellets. The intrinsic viscosity before solid phase polymerization was 0.76 dl / g. The content of acetaldehyde contained in the chip after freeze-disintegration of the blend chip was 35.0 ppm.
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| WO2021066284A1 (en) * | 2019-10-01 | 2021-04-08 | 에스케이케미칼 주식회사 | Polyester resin blend and molded article formed therefrom |
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| KR0134657B1 (en) * | 1994-10-12 | 1998-04-20 | 박홍기 | Method for manufacturing copolyester |
| KR0143044B1 (en) * | 1993-12-27 | 1998-07-15 | 박홍기 | The process of preparation of polyester composition |
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| WO2020141916A1 (en) * | 2019-01-04 | 2020-07-09 | 황재순 | Construction material containing coffee grounds, and manufacturing method therefor |
| WO2021066284A1 (en) * | 2019-10-01 | 2021-04-08 | 에스케이케미칼 주식회사 | Polyester resin blend and molded article formed therefrom |
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